Condensation of haloaromatic compounds with carbohydrates and related materials



CONDENSATION OF HALOAROMATIC C POUNDS WITH CARBOHYDRATES AND RE- LATED MATERIALS Carl B. Linn, Riverside, 11]., assignor, by mesne assignments, to Universal Oil Products Company, Des Plaines, 11]., a corporation of Delaware No Drawing. Application June 18',1957' Serial No. 666,486

6 Claims. (Cl. 260'-345.9)

This application is a continuation-in-part of my copendmg application Serial No. 401,068, filed December 29, 1953, now Patent No. 2,798,079.

This invention relates to a process for interacting haloaromatic compounds with carbohydrates and materials closely related to carbohydrates. The process relates more particularly to the condensation of simple sugars, their desoxyand omega-carboxy derivatives, compound sugars or oligosaccharides, and polysaccharides, with haloaromatic compounds in the presence of a hydrogen fluoride catalyst.

An object of this invention is to produce organic materials suitable for use per se or as intermediates in the manufacture of detergents, pharmaceuticals, explosives, gelling agents, surface coatings, resins, and corrosion inhibitors by condensing haloaromatic compounds with carbohydrates or with carbohydrate derivatives.

One embodiment of this invention relates to a process which comprises condensing a haloaromatic compound with a carbohydrate in the presence of a hydrogen fluor1de catalyst to produce a compound selected from the group consisting of a haloaryl-desoxy-alditol and a haloaryl-desoxy-ketitol, and recovering said resultant condensation product.

A specific embodiment of this invention relates to a process which comprises condensing chlorobenzene with glucose in the presence of a hydrogen fluoride catalyst to produce a l-(chlorophenyl)-1-des0xy-glucitol, and re covering said resultant condensation product.

I have found that useful water-insoluble condensation products and also water-soluble condensation products are formed by interacting haloaromatic compounds with carbohydrates and related substances in the presence of a hydrogen fluoride catalyst. These reactions may be carried out in steel equipment or other suitable apparatus lined with silver, copper, and certain alloys such as Monel metal and the like. The treatment may be eifected at temperatures of from about -40 to about 100 C. and preferably at temperatures of from about -10 to about |50 C. The pressure at which the reaction is carried out will vary with the reaction temperature used and mol fractions of reactants and hydrogen fluoride catalyst present. While many of the condensation reactions are carried out at substantially atmospheric pressure, it may be desirable in certain instances and with certain reactants to carry out the reaction at pressures up to about 100 atmospheres or more. It is convenient in most instances to operate the equipment utilized at the pressure generated by the reaction mixture and the catalyst contained therein.

Haloaromatic compounds which may be used as starting materials in the process of this invention include fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, ortho-chlorotoluene, meta-chlo-rotoluene, parachlorotoluene, ortho-chloroethylbenzene, meta-chloroethylbenzene, para-chloroethylbenzene, ortho-dichlorobenzene, para-dichlorobenzene, 1,2,4-trichlorobenzene, paradibromobenzene, orthobrornochlorobenzene, paras-bromores Patent ice naphthalene, alpha-brornonaphthalene, etc.

Carbohydrates which are condensed with haloaromatic compounds in the process of the present invention to form a compound selected from the group consisting of a haloaryl-desoxy-alditol and ahaloaryl-desoxy-ketitol' in clude simple sugars, their desoxyand omega-carboxy' derivatives, compound sugars or oligosaccharides, and polysaccharides. v 7

Simple sugars include dioses, trioses, tetroses, pentoses, hexoses, heptoses, octoses, nonoses, and decoses. Com pound sugars include disaccharides, trisaccharides, and tetrasaccharides. Polysaccharides include polysaccharides composed of only one type of sugar residue, polysaccharides composed of more than one" type of sugar" unit, polysaccharides composed of one type of uronic'acid unit, i.e., polyuronides, polysaccharides composed of aldose (pentose or hexose) and uronic acid units, po1ysaccharides containing hexose units esterified with an inorganic acid, and polysaccharides containing amino sugar units. I D Utilizable simple sugars include the dios e, glycolaldehyde; trioses, such as glycerylaldehyde and s-dihydroxy-acetone; tetroses, such as erythrose, threose, erythrulose, and apiose; the pentoses, such as arabinose, xylose, ribose, lyxose, rhamnose (a methylp'entose), fucose (a methylpentose), rhodeose (a methylp'entose), digitalose (a methoxymethylpentose), ketoxylose (a ketopentose), Z-desoxy-ribose and 2-desoxy-methylpentose (digotoxose); hexoses, s'uchas mannose, glucose, idose, gulose, galactose, talose, allose, fructose,- sorbose, tagatose, and psicose; heptoses, such as glucohept'ose, mannoheptose, galactoheptose, sedoheptose, mannoketoheptose, glucoheptulose and perseulose; octoses, such as glucoocto'se, mannooctose, and galactooctose; nonoses,

such as glucono'nose, and mannononose; and decos'es such as glucodecose. Desoxy derivatives of simple sugars are formed by the replacement of a hydroxyl substituent in a sugar with" hydrogen thereby forming a methyl or methylene linkage. The desoxypentoses and" desoxyhexoses are the most commonly occurring of such cornpounds. The omega-carboxy derivatives of simplesugars, which are suitable in the process of'the present invention include tartronic semialdeliyde or its tautomer, hydroxypyruvic acid; alpha-gamma-dihydroxyacetoacetic acid, threuronic acid, 4-keto-2,3,5-trihydroxypentanoic acid, xyluronic acid, 5 keto-tetrahydroxyhexanoic acids such as S-keto-allonic acid, S-keto-gluconie acid, S-ketomannonic acid, 5keto-gulom'c acid, and S-keto-galactbnic acid; uronic acids containing 6 carbon atoms such as glucuronic acid, mannuronic acid, and galacturonic acid, and the 6-keto-pentahydroxyheptanoic acids. The simple sugars and their omega-.carboxy derivatives, as starting materials for the process of this invention, maybe represented by the following general formula:

n= 1, and B=H, the compoundis sdihydroxyacetone; Y

Patented Feb. 23, 19 0 when A=CH OH, n= 1, and B=CH OH, the compound is erythrulose; when A=CH OH, n=1, and B=COOH, the compound is alpha-gamma-dihydroxyacetoacetic acid; when A=H, n=2, and B=CH OH, the compound is erythrose or threose; when A=H, n=2, and B=COOH, the compound is threuronic acid; when A=CH OH, n=2, and B=CH OH, the compound is riboketose or xyloketose; when A=CH OI-I, n=2, and B=COOH, the compound is a 4-keto-2,3,5-trihydroxypentanoic acid; when A=H, n=3, and B=CH OH, the compound is ribose, arabinose, xylose or lyxose; when A=H, n=3, and B=COOH, the compound is a 5 carbon atom uronic acid such as xyluronic acid; when A=CH OH, n=3, and B=CH OH, the compound is psicose, fructose, sorbose, or tagatose; when A=CH OH, n=3, and B=COOH, the compound is a S-keto-tetrahydroxyhexanoic acid; when A=H, n=4, and B=CH OH, the compound is allose, altrose, glucose, mannose, gulose, idose, galactose, or talose; when A=H, n=4, and B=COOH, the compound is a 6 carbon atom uronic acid such as glucuronic acid, mannuronic acid, and galacturonic acid; when A=CH OH, n=4, and B==CH OH, the compounds are heptoses; and when A=CH OH, n=4, and 'B=COOH, the compounds are 6-keto-pentahydroxyheptanoic acids.

The utilizable oligosaccharides or compound sugars include disaccharides such as the pentose-hexose disaccharides including glucoapiose, vicianose and primeverose; the methylpentose-hexose disaccharides including glycorhamnoside, and rutinose; and the dihexoses such as turanose, maltose, lactose, cellobiose, gentiobiose, melibiose, sucrose, and trehalose. Other compound sugars are represented by trisaccharides such as the methylpentose-hexose saccharides including rhamninose and robinose; the tn'hexose saccharides including raflinose, melezitose, and gentianose. An example of a suitable tetrasaccharide is stachyose.

Various polysaccharides are also utilizable in the process of the present invention. These polysaccharides include pentosans such as araban, methylpentosans such as fucosan, and hexosans such as starch, cellulose, glycogen, inulin, mannan, galactan, lichenin, levan, dextran, and laminarin. Other polysaccharides which are composed of more than one type of sugar unit such as pentosans like araboxylan, and the hexosans like galactomannan may be used. Other utilizable polysaccharides are represented by those composed of uronic acid units and aldose units such as gum arabic, damson gum, gum tragacanth, linseed mucilage, and pectins, those composed of uronic acid units such as pectic acid and alginic acid, and those containing hexose units esterified with an inorganic acid such as certain sea weed polysaccharides like agar.

The hydrogen fluoride catalyst which is used in this process may be used in anhydrous form or diluted with water to make a hydrofluoric acid of the desired concentration. The hydrofluoric acid may also be further diluted with various inert diluents when it is desirable to operate the process of this invention with low hydrogen fluoride concentrations. Suitable inert diluents include the perfluoro derivatives of n-paraflinic hydrocarbons such as perfluoropropane, perfluoro-n-butane, perfluoron-pentane, perfiuoro-n-hexane, etc. Other suitable diluents are well known to those skilled in the art, for example, cycloparaflins such as cyclopentane or cyclohexane may be utilized. In some instances, hydrofluoric acid of from about 85 to about 100% HP concentration is desirable, and in some other instances it is most desirable to use anhydrous hydrogen fluoride as the catalyst.

The process may be carried out by slowly adding a hydrogen fluoride catalyst to a stirred mixture of halo- 4 aromatic compound and carbohydrate or related material being subjected to reaction while maintaining the reaction temperature at from about 40 to about 100 C. by

- suitable cooling and/or heating means. It is often desirable or advisable to commingle the reactants and catalyst at relatively low temperatures such as from about 4 to about 30 C. and then to permit the reaction mixture to warm gradually while the reactants and catalyst are stirred by suitable means such as a motor driven stirrer or other adequate mixing equipment. After the reaction has reached the desired degree of completion, the hydrogen fluoride catalyst is removed from the reaction mixture by distillation at atmospheric or' lower pressures, or by passing an inert gas through the reaction mixture while maintaining it at a relatively low temperature. Also the entire reaction mixture and catalyst may be mixed with water or may be added to ice in order to quench the activity of the hydrogen fluoride catalyst and to permit separation of the organic reaction products and unreacted starting materials from the catalyst. The organic reaction products may also be separated from aqueous hydrogen fluoride by means of an organic solvent such as ether, in which some of the organic material may be dissolved. Further means of isolating the reaction products are illustrated in the examples. Thus the product formed by reacting chlorobenzene withglucose or cellulose in the presence of substantially anhydrous hydrogen fluoride at 30 C. separated into an ether-soluble and water-insoluble product and an ether-insoluble and water-soluble product. 7

The process of this invention broadly emphasizes the reaction of carbohydrates including simple sugars, their derivatives, compound sugars, and polysaccharides with haloaromatic compounds using as a catalyst hydrogen fluoride. The type of product obtained is markedly affected by the length of time that the reactants are in contact with the hydrogen fluoride catalyst as well as the temperature of the reaction. The reaction products of this process lead to materials having diversified uses. For example, some of the reaction products can be used per se as surface coating materials as, for example, thermoset ting resins which can be prepared simply by heating. Resins can also be made by heating the reaction products with formaldehyde, urea, phenol, aniline, etc. and cornbinations of the above enumerated compounds. Nitration of many of the reaction products will give explosives. These explosives will contain nitro groups attached to the aromatic rings as well as being nitric acid esters or nitroalcohol derivatives. Various reaction products are eifective for gelling paraffinic or aromatic hydrocarbons. Other reaction products are useful per se or as intermediates in the preparation of corrosion inhibitors. The nature of this invention is illustrated further by the following examples, which however, should not be construed to limit unduly the generally broad scope of this invention.

Examplel This example illustrates the reaction of a haloaromatic compound, namely chlorobenzene, with a carbohydrate, namely cellulose. Cellulose is a polysaccharide containing glucoside linkages and with all but one of the poten tial aldehyde groups of the glucose residues involved in these glucosides.

As an example of the manner of conducting these experiments, the following detailed description is given: In a one liter steel turbomixer autoclave is sealed 41 grams of cellulose and 72 grams of chlorobenzene. With stirring, the autoclave is then cooled to 78 C. and about 220 grams of hydrogen fluoride is added. The temperature is allowed to rise to 10 C. and the reactants are then contacted at this temperature for 36 hours. Then, a stream of nitrogen is passed through the reactor at room temperature to remove most of the hydrogen fluoride. A substantial amount of hydrogen fluoride remains behind in the reaction mixture, although most of it can be removed by prolonging the nitrogen purge. The autoclave is opened and the product is found to be a heavy fuming brown syrup. This is then poured into a silver dish and depending upon the amount of hydrogen fluoride remaining therein weighs from about to about grams. After standing for several days in a hood-draft,

the product solidifies. This'rnas's is thenmas'c'erated with large quantities of cold water to remove unreacted carbohydrate, if any. During the process, the cellulose is broken down into glucose residues which become soluble in cold water. The cold water insoluble portion of the product is treated with boiling water which after cooling and reduction in volume yields a chemical individuali'corresponding to 1,1-di-(chlorophenyl)-1-desoxy-glucitbl o the following formula:

HOH

HOE

HOH

CHOH JHrOH This product may be recrystallized from a 50% ethanol solution.

Example 11 This experiment again illustrates the reaction of a carbohydrate, namely glucose, with a haloaromatic compound. In this example 40 grams of glucose, 72 grams of chlorobenzene, and about 225 grams of hydrogen fluoride are utilized. The procedure utilized in this example is the same as that described hereinabove in Example I down through allowing the product to stand in a draft. To this crude product is added one liter of ethyl ether and the mixture is allowed to stand for two days. The other is then decanted oif and the residue is dissolved in 500 ml. of hot 50% ethanol. This alcohol solution is filtered While hot and is then allowed to stand at 0 C. The material which separates at this point corresponds to the 1,1-di(chlorophenyl)-l-desoxy-glucitol described in Example I.

The more soluble part of the product is believed to contain a mono-chlorophenyl-glucitol corresponding to the following structural formula:

Example III In this example, glucose is reacted with ortho-chlorotoluene. The experiment is carried out in a steel turbomixer autoclave as described in Example I, the charge being 81 grams of ortho-chlorotoluene, 40 grams of glucose, and about 225 grams of hydrogen fluoride. The ortho-chlorotoluene and glucose are sealed into the autoclave which is then cooled to about 30 C. at which temperature the hydrogen fluoride is added. The temperature of the autoclave is then brought to 45 C. and is kept there for 12 hours during which time the mixture is stirred. Then, while continuing the stirring, a stream of nitrogen is passed through the autoclave for about 3 hours. The reaction product is washed several times with portions of cold water. The cold water insoluble product is boiled in hot water, the hot water solution is filtered,

ill)

andthdil'tfate-is-tlien set aside to cue-1: After 'staiiding (anon "H011 drron j l (hon.

hmon In thisv example; glucose is reacted with ortho-bromotoluene. The experiment is carried out in av steel turbo mixer autoclaveas. described; in. Exa'mple ,I, the charge being 101 grams of ortho-bromotoluene, 40 grams of glucose, and about 225 grams of hydrogen fluoride. The ortho-bromotoluene and glucose are sealed into the autoclave which is then cooled to about -30 C. at which temperature the hydrogen fluoride is added. The temperature of the autoclave is then brought to 30 C. and is kept there for 12 hours during which time the mixture is stirred. Then, while stirring the mixture, a stream of nitrogen is passed through the autoclave for about 3 hours. The reaction product is washed with several portions of water. The remaining reaction product is dissolved in boiling water, filtered, and set aside to cool. After standing for about 5 hours at 0 C., a material was recovered which, after recrystallization, is found to have the following structural formula:

(IJHs Example V In this example, starch is reacted with alpha-chloronaphthalene. This experiment is carried out in a steel turbomixer autoclave as described in Example I, the charge being 104 grams of alpha-chloronaphthalene, 40 grams of starch, and about 220 grams of hydrogen fluoride. The alpha-chloronaphthalene and starch are sealed into the autoclave which is then cooled to about --40 C. at which temperature the hydrogen fluoride is added. The temperature of the autoclave is then brought to 55 C. and maintained there for 5 hours time during which time the reaction mixture is stirred continually. Then, a stream of nitrogen is passed through the autoclave for about 6 hours. The reaction product is washed with several portions of cold water and then is mascerated with boiling water. The hot water solution is allowed to cool and is set aside at 0 C. From this cold solution a new chemical entity is recovered. After recrys- 7 tallization, a product is isolated of the following struct'ural formula:

C1 Cl 8 alyst at a temperature of from about C. to about C.

3. A process which comprises reacting chlorobenzene with glucose in the presence of hydrogen fluoride catalyst at a temperature of from about 40 C. to about 100 C.

4. A process which comprises vreacting ortho-chlorotoluene with glucose in the presence of hydrogen fluoride catalyst at a temperature of from about -40 C. to about 100 C.

5. A process which comprises reacting bromobenzene with glucose in the presence of hydrogen fluoride catalyst at a temperature of from about 40 C. to about 100 C.

6. A process which comprises reacting alpha-chloronaphthalene with starch in the presence of hydrogen fluoride catalyst at a temperature of from about 40 C. to about 100 C.

References Cited in the file of this patent UNITED STATES PATENTS Niederl Aug. 19, 1941 Linn July 2, 1957 OTHER REFERENCES 

1. A PROCESS WHICH COMPRISES REACTING A HALOAROMATIC HYDROCARBON SELECTED FROM THE GROUP CONSISTING OF HALOBENZENE, HALO-METHYLBENZENE, HALO-ETHYLBENZENE AND HALONAPHTHALENE WITH A CARBOHYDRATE SELECTED FROM THE GROUP CONSISTING OF MONOSACCHARIDES, OLIGOSACCHARIDES, AND POLYSACCHARIDES, IN THE PRESENCE OF HYDROGEN FLUORIDE CATALYST AT A TEMPERATURE OF FROM ABOUT -40*C. TO ABOUT 100*C. 